Polyetheramines based on 1,3-dialcohols

Abstract

This invention relates to polyetheramines based on 1,3-dialcohols, in particular to an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of anamine of Formula (I) and/or (II), wherein R 1 -R 12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R 1 -R 6 and at least one of R 7 -R 12 is different from H, wherein A 1 -A 9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, preferably 2-10 carbon atoms, most preferably 2-5 carbon atoms, wherein Z 1 -Z 4 are independently selected from OH or NH 2 , wherein at least one of Z 1 -Z 2 and at least one of Z 3 -Z 4 is NH 2 , and wherein the sum of x+y is in the range of from 2 to 200, wherein x≥1 and y≥1; and x 1 +y 1 is in the range of from 2 to 200, preferably 2-20, most preferably 2-10, wherein x 1 ≥1 and y 1 ≥1.

The invention claimed is: 
     
       1. An etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an amine of Formula (I) and (II), 
       
         
           
           
               
               
           
         
       
       wherein R 1 -R 12  are independently H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R 1 -R 6  and at least one of R 7 -R 12  is not H,
 wherein A 1 -A 9  are independently linear or branched alkylenes having 2 to 18 carbon atoms, 
 wherein Z 1 -Z 4  are independently OH, NH 2 , NHR′ or NR′R″, wherein at least one of Z 1 -Z 2  and at least one of Z 3 -Z 4  is NH 2 , NHR′ or NR′R″, wherein R′ and R″ are independently alkylenes having 2 to 6 carbon atoms and wherein the sum of x+y is in the range of from 3 to 20, 
 wherein x≥1 and y≥1; and x 1 +y 1  is in the range of from 2 to 200, wherein x 1 ≥1 and y 1 ≥1. 
 
     
     
       2. The etheramine mixture according to  claim 1 , wherein the etheramine mixture comprises at least 95% by weight, based on the total weight of the etheramine mixture, of the amine of Formula (I) and (II). 
     
     
       3. The etheramine mixture according to  claim 1 , wherein in said polyetheramine of Formula (I) or Formula (II), the degree of amination is in the range of 60% to 100%. 
     
     
       4. The etheramine mixture according to  claim 1 , wherein in said polyetheramine of Formula (I) or Formula (II), A 1 -A 9  are independently selected from the group consisting of ethylene, propylene, and butylene. 
     
     
       5. The etheramine mixture according to  claim 1 , wherein in said polyetheramine of Formula (I) or Formula (II), each of A 1 -A 9  is propylene. 
     
     
       6. The etheramine mixture according to  claim 1 , wherein in said polyetheramine of Formula (I) or Formula (II), R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 11 , and R 12  are H and R 3 , R 4 , R 9 , and R 10  are independently C1-16 alkyl or aryl. 
     
     
       7. The etheramine mixture according to  claim 1 , wherein in said polyetheramine of Formula (I) or Formula (II), R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 11 , and R 12  are H and R 3 , R 4 , R 9 , and R 10  are independently a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group. 
     
     
       8. The etheramine mixture according to  claim 1 , wherein in said polyetheramine Formula (I) or Formula (II), R 3  and R 9  are each an ethyl group, R 1 , R 2 , R 5  R 6 , R 7 , R 8 , R 11 , R 12  are each H, R 4  and R 10  are each a butyl group. 
     
     
       9. The etheramine mixture according to  claim 1 , wherein the polyetheramine of Formula (I) or Formula (II) has a weight average molecular weight of about 290 to about 1000 grams/mole. 
     
     
       10. A process for the manufacture of an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an etheramine of Formula (I) and (II) comprising the following steps:
 a) reacting a 1,3-diol of Formula (III) with C 2 -C 18  alkylene oxides, wherein the molar ratio of 1,3-diol to C 2 -C 18  alkylene oxides is in the range of 1:3 to 1:8, 
 
       
         
           
           
               
               
           
         
         wherein R 1 -R 6  are independently of one another H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl and at least one group selected from R 1 -R 6  is not H, to form an alkoxylated 1,3-diol; and 
         b) aminating the alkoxylated 1, 3-diol with ammonia. 
       
     
     
       11. The process for the manufacture of an etheramine mixture according to  claim 10 , further comprising reacting the polyetheramine of Formula (I) or Formula (II) obtained in step b) with an acid. 
     
     
       12. The process according to  claim 10 , wherein the molar ratio of 1,3-diol to C 2 -C 18  alkylene oxides is in the range of 1:3 to 1:8. 
     
     
       13. The process according to  claim 10 , wherein the molar ratio of 1,3-diol to C 2 -C 18  alkylene oxides is in the range of 1:4 to 1:6. 
     
     
       14. The process according to  claim 10 , wherein the C 2 -C 18  alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. 
     
     
       15. The process according to  claim 10 , wherein the C 2 -C 18  alkylene oxide is propylene oxide. 
     
     
       16. The process according to  claim 10 , wherein the 1,3-diol of formula (III) is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-phenyl-1,3-propanediol, 2,2-dimethyl-1,3-propandiol, and 2-ethyl-1,3-hexandiol. 
     
     
       17. The process according to  claim 10 , wherein the amination is carried out in the presence of a copper-, nickel- or cobalt-containing catalyst. 
     
     
       18. The process according to  claim 17 , wherein the catalytically active material of the catalysts, before the reduction thereof with hydrogen, comprises oxygen compounds of aluminum, of copper, of nickel and of cobalt, and in the range from 0.2 to 5.0% by weight of oxygen compounds of tin, calculated as SnO. 
     
     
       19. A shampoo or body wash formulation comprising the etheramine mixture of  claim 1 . 
     
     
       20. A curing agent for epoxy resins or a reactant in the production of polymers comprising the etheramine mixture of  claim 1 . 
     
     
       21. The etheramine mixture of  claim 1 , wherein A 1 -A 9  are independently linear or branched alkylenes having 2 to 10 carbon atoms. 
     
     
       22. The etheramine mixture of  claim 1 , wherein A 1 -A 9  are independently linear or branched alkylenes having 2 to 5 carbon atoms. 
     
     
       23. The etheramine mixture of  claim 1 , wherein x 1 +y 1  is in the range of from 2 to 20. 
     
     
       24. The etheramine mixture of  claim 1 , wherein x 1 +y 1  is in the range of from 2 to 10.